Recent advances on tailor-made titanium catalysts for biopolymer synthesis

• State-of-the-art of well-defined titanium complexes for biopolymer synthesis such as polyesters, polycarbonates, poly(methyl metacrylate) derivatives and copolymers are reviewed.
• Use of titanium complexes as catalysts in the ring-opening polymerization, α-olefin polymerization and polycondensation reactions.
• Influence of titanium complexes bearing ancillary ligands on the catalytic activity and stereoselectivity are discussed.

After years of influence of titanium-based Ziegler–Natta catalysts on “petropolymers” synthesis, titanium complexes are experiencing a resurgence in research efforts as sustainable catalysts for biopolymer synthesis. This review article summarizes the different classes of well-defined homogeneous and heterogeneous titanium catalysts supported by various multidentate ancillary ligands for the synthesis of polyesters, polycarbonates and poly(methyl metacrylate) derivatives which are biodegradable and/or synthesized from renewable monomers. Special attention is given to the relationships between the electronic and steric effects of catalysts governing the activity, control and stereoselectivity whenever applicable.

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